Conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene

ABSTRACT

Described is a method for producing fluoropropenes of formula CF 3 CX═CX 2  wherein each X is F or H, at least one X is H, and at least one X is F, comprising pyrolyzing a hydrofluorochloropropane of formula CF 3 CXYCX 2 Y, wherein each X is F or H, at least one X is H, and at least one X is F, and one Y is Cl and the other Y is H, in the gas-phase in a reaction vessel, maintained at a temperature high enough to effect the pyrolysis of said hydrofluorochloropropane to said fluoropropene, wherein the selectivity for the production of the fluoropropene is at least 80%, in the absence of a catalyst.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a continuation-in-part of U.S. application Ser. No. 12/605,573, filed Oct. 26, 2009, which claims the benefit of priority of U.S. Provisional Applications 61/108,585, filed Oct. 27, 2008, and 61/121,248, filed Dec. 10, 2008.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to methods of synthesis of fluorinated olefins.

2. Description of the Related Art

The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents and propellants. These new compounds, such as HFC refrigerants, HFC-134a and HFC-125 being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase-out as a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials. Certain hydrofluoroolefins are believed to meet both goals. Thus there is a need for manufacturing processes that provide halogenated hydrocarbons and fluoroolefins that contain no chlorine that also have a low global warming potential.

SUMMARY

Described is a method for producing a fluoropropene of formula CF₃CF═CH₂, comprising pyrolyzing a hydrofluorochloropropane of formula CF₃CFClCH₃, in the gas-phase in a reaction vessel, maintained at a temperature of from about 400° C. to 700° C., wherein the selectivity for the production of the fluoropropene is at least 80%, in the absence of a catalyst.

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.

DETAILED DESCRIPTION

Described is a method for producing fluoropropenes of formula CF₃CX═CX₂ wherein each X is F or H, at least one X is H, and at least one X is F, comprising pyrolyzing a hydrofluorochloropropane of formula CF₃CXYCX₂Y, wherein each X is F or H, at least one X is H, and at least one X is F, and one Y is Cl and the other Y is H, in the gas-phase in a reaction vessel, maintained at a temperature high enough to effect the pyrolysis of said hydrofluorochloropropane to said fluoropropene, wherein the selectivity for the production of the fluoropropene is at least 80%, in the absence of a catalyst.

Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.

Before addressing details of embodiments described below, some terms are defined or clarified.

As used herein, the terms pyrolyzing and pyrolysis refer to the decomposition or breaking down of a material or compound due to heat in the absence of oxygen or any other reagents.

As used herein, reaction vessel refers to any vessel in which the reaction may be performed in either a batchwise mode, or in a continuous mode. Suitable vessels include batch reactor vessels, or tubular reactors.

In one embodiment, the reaction vessel is comprised of materials which are resistant to corrosion including stainless steel, Hastelloy, Inconel, Inconel 600, Inconel 625, Hastelloy C, Hastelloy B1 Hastelloy B2, Monel, gold, or gold-lined, quartz or nickel.

As used herein, percent selectivity is defined as the weight of a desired product formed, as a fraction of the total amount of the products formed in the reaction, and excluding the starting chlorofluorocarbon.

As used herein, percent conversion is defined as 100%, less the weight percent of starting hydrofluorochloropropane in the effluent from the reaction vessel.

The hydrochlorofluoropropane described herein has the formula CF₃CXYCX₂Y, wherein each X is F or H, at least one X is H, and at least one X is F, and one Y is Cl and the other Y is H. A fluoropropene as described herein has the formula CF₃CX═CX₂ wherein each X is F or H, at least one X is H, and at least one X is F. Representative hydrochlorofluoropropanes include 1,1,1,2-tetrafluoro-2-chloropropane, 1,1,1,2-tetrafluoro-3-chloropropane, 1,1,1,3-tetrafluoro-2-chloropropane, 1,1,1,3-tetrafluoro-3-chloropropane, 1,1,1,2,3-pentafluoro-2-chloropropane, 1,1,1,2,3-pentafluoro-3-chloropropane, 1,1,1,3,3-pentafluoro-2-chloropropane and 1,1,1,3,3-pentafluoro-3-chloropropane.

Representative fluoropropenes include 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene and 1,1,3,3,3-pentafluoropropene.

In one embodiment, the hydrochlorofluoropropane is 1,1,1,2-tetrafluoro-2-chloropropane and the fluoropropene is 2,3,3,3-tetrafluoropropene. In another embodiment, the hydrochlorofluoropropane is 1,1,1,2-tetrafluoro-3-chloropropane and the fluoropropene is 2,3,3,3-tetrafluoropropene. In yet another embodiment, the hydrochlorofluoropropane is 1,1,1,3-tetrafluoro-2-chloropropane and the fluoropropene is 1,3,3,3-tetrafluoropropene. In yet another embodiment, the hydrochlorofluoropropane is 1,1,1,3-tetrafluoro-3-chloropropane and the fluoropropene is 1,3,3,3-tetrafluoropropene. In yet another embodiment, the hydrochlorofluoropropane is 1,1,1,2,3-pentafluoro-2-chloropropane and the fluoropropene is 1,2,3,3,3-pentafluoropropene. In yet another embodiment, the hydrochlorofluoropropane is 1,1,1,2,3-pentafluoro-3-chloropropane and the fluoropropene is 1,2,3,3,3-pentafluoropropene. In yet another embodiment, the hydrochlorofluoropropane is 1,1,1,3,3-pentafluoro-2-chloropropane and the fluoropropene is 1,1,3,3,3-pentafluoropropene. In yet another embodiment, the hydrochlorofluoropropane is 1,1,1,3,3-pentafluoro-3-chloropropane and the fluoropropene is 1,1,3,3,3-pentafluoropropene.

In one embodiment, fluoropropenes are prepared by thermal dehydrochlorination of hydrochlorofluoropropanes. This reaction occurs selectively, in the absence of a catalyst. In one embodiment, a hydrochlorofluoropropane is introduced into a reaction vessel wherein the temperature is maintained at a temperature high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane. In one embodiment, the temperature is high enough to effect the thermal dehydrochlorination to a percent conversion of at least 20%. In another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 50%. In another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 65%. In yet another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 80%. In yet another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 70% for at least 12 hours of continuous operation.

In one embodiment, the hydrochlorofluoropropane is introduced into a reaction vessel wherein the temperature is maintained at a temperature in the range of from about 400° C. to about 700° C. In another embodiment, the temperature of the reaction vessel is maintained in the range from about 400° C. to about 600° C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the the pyrolysis of the hydrochlorofluoropropane to fluoropropene with a selectivity of 80% or greater. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the pyrolysis of the hydrochlorofluoropropane to the fluoropropene with a selectivity of 85% or greater.

In one embodiment, the reaction vessel is comprised of materials which are resistant to corrosion. In one embodiment, these materials comprise alloys, such as stainless steel, Hastelloy, Inconel, Inconel 600, Inconel 625, Hastelloy C, Hastelloy B1 Hastelloy B2, Monel, gold, or gold-lined, quartz or nickel.

In one embodiment, the hydrochlorofluoropropane is preheated in a vaporizer to a temperature of from about 30° C. to about 100° C. In another embodiment, the hydrochlorofluoropropane is preheated in a vaporizer to a temperature of from about 30° C. to about 80° C.

In some embodiments, an inert diluent gas is used as a carrier gas for the hydrochlorofluoropropane. In one embodiment, the carrier gas is selected from nitrogen, argon, helium or carbon dioxide.

In one embodiment the reaction vessel is of a design commonly referred to as a shell and tube reactor. In one embodiment, heat input into the reaction is provided through the use of a superheated diluent gas to provide sufficient heat input into the reactor and incoming raw materials.

The reaction pressure can be subatmpospheric, atmospheric or superatmostpheric. In one embodiment, the reaction is conducted at a pressure of from 14 psig to about 100 psig. In another embodiment, the reaction is conducted at a pressure of from 14 psig to about 60 psig. In yet another embodiment, the reaction is conducted at a pressure of from 40 psig to about 85 psig. In yet another embodiment, the reaction is conducted at a pressure of from 50 psig to 75 psig.

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of the elements use the “New Notation” convention as seen in the CRC Handbook of Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

EXAMPLES

The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.

Legend

HFC-244bb is 2-chloro-1,1,1,2-tetrafluoropropane

HFO-1234yf is 2,3,3,3-tetrafluoropropene

HCFO-1233xf is 2-chloro-3,3,3-trifluoropropene

Example 1

Example 1 demonstrates the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst.

An empty inconel tube (½ inch OD) with a heated zone of about 12 inches was heated to a temperature between 500° C. and 626° C., and HFC-244bb was fed at 0.52 ml/hour through a vaporizer set at 40° C. using a N₂ sweep of 2.4 sccm (4.0×10⁻⁸ m³). The reactor effluent was analyzed using an on-line GCMS, with the results being reported in mole percent. Results for percent conversion, percent selectivity, and operating temperature are reported in Table 1, below.

TABLE 1 Conversion Selectivity Selectivity Temp ° C. of 244bb to 1234yf to 1233xf 500 16.2% 80% 8% 550 65.4% 88% 2% 574 86.4% 88% 2% 601 99.6% 85% <1%  626 99.8% 83% 1%

Example 2

Example 2 demonstrates the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst.

An empty inconel tube (½ inch OD) with a heated zone of about 12 inches was heated to 575° C., and HFC-244bb was fed at 0.35 ml/hour through a vaporizer set at 40° C. using a N₂ sweep of 3.6 sccm (6.0×10⁻⁸ m³). The reactor was operated for a total of 19 hours continuously, and samples were taken periodically and analyzed to determine % conversion of HFC-244bb, and selectivity to HFO-1234yf. The reactor effluent was analyzed using an on-line GCMS, and the data in Table 2 below is an average of at least two on-line injections at a given condition; the percentages are mole percent. The data in Table 2 show the performance of this reaction to make HFO-1234yf via HCl elimination over the period of 19 hours of operation.

TABLE 2 Conversion Selectivity Selectivity Hours of 244bb to 1234yf to 1233xf 3 80% 84%  6% 4 75% 80% 9.7%  8 81% 72% 17% 12 81% 70% 20% 15 82% 78% 14% 19 85% 73% 19.6% 

Example 3

Example 3 demonstrates the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst in a gold-lined tube.

An empty gold-lined tube (½ inch OD) with a heated zone of about 12 inches was heated to a temperature about 550° C., and HFC-244bb was fed at 0.75 ml/hour through a vaporizer set at 40° C. using a N₂ sweep of 3.75 sccm (6.25×10⁻⁸ m³). The reactor effluent was analyzed using an on-line GCMS, with the results being reported in mole percent. Results for percent conversion, percent selectivity, and operating temperature are reported in Table 3, below.

TABLE 3 Conversion Selectivity Selectivity Temp ° C. of 244bb to 1234yf to 1233xf 550 72% 94% 2%

Example 4

Example 4 shows the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst at 480° C.

A mixture of 99% of 244bb and 1% of 1233xf was passed through a ½″×12″ (ID 0.334″) Inconel 625 tube with flow rates of 2.4 ml/hr, 1.2 ml/hr, 0.8 ml/hr and 0.4 ml/hr at 480° C. at 1 atmosphere pressure. The stream from the reactor was analyzed by GC and GC-MS. The result of the test is listed in Table 4 below. The reaction shows high selectivity to 1234yf and low selectivity to 1233xf.

TABLE 4 Flow rate 2.4 ml/hr 1.2 ml/hr 0.8 ml/hr 0.4 ml/hr % 1234yf 22 31 38 51 % 244bb 76 67 59 47 % 1233xf 1 1 1 1

Example 5

Example 5 illustrates long reactor life in the dehydrochlorination of 244bb in the absence of hydrogen fluoride.

A mixture of 99% of 244bb and 1% of 1233xf was passed through a ½″×12″ (ID 0.334″) Inconel 625 tube for dehydrochlorination at a flow rate of 1 ml/hr. The 244bb used in this reaction was scrubbed by deionized water and contained no detectable HF. The stream from the reactor was analyzed by GC and GC-MS. The result of the test is listed in Table 5 below. The reaction shows high selectivity to 1234yf and low selectivity to 1233xf out to 2000 hours of operation.

TABLE 5 Time (hr) % 1234yf % 1233xf % 244bb Temp (° C.) 600 24.1 1.0 74.6 440 1500 29.0 1.1 69.5 445 2002 24.0 1.1 74.6 446

Example 6

This example demonstrates the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst at 435° C. with 50 psig back pressure.

An empty Inconel tube (½ inch OD, 0.334″ ID) with a heated zone of about 12 inches was heated to 435° C., and HFC-244bb was fed at 1 ml/hour through a vaporizer set at 40° C. The reactor was operated at 50 psig backpressure and at this condition for 280 hours continuously, and samples were taken periodically and analyzed to determine % conversion of HFC-244bb, and selectivity to HFO-1234yf. The reactor effluent was analyzed using an on-line GCMS, and the data were listed in Table 6 below; the percentages are mole percent. The data in Table 6 below show the performance of this reaction to make HFO-1234yf via HCl elimination over the period of 283 hours of operation.

TABLE 6 Conversion Selectivity Selectivity Back pressure Hours of 244bb to 1234yf to 1233xf Psig 2 25.90% 98.21% 0.20% 49.9 40 24.22% 98.18% 0.20% 50.9 80 23.02% 98.18% 0.18% 49.9 120 24.54% 98.21% 0.17% 50.9 200 23.06% 98.22% 0.20% 49.9 280 23.00% 98.44% 0.44% 49.5

Example 7

This example demonstrates the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst at 460° C. with 1.2 psig and 50 psig back pressure.

An empty Inconel tube (½ inch OD, 0.334″ ID) with a heated zone of about 12 inches was heated to 460° C., and HFC-244bb was fed at 1.2 ml/hour through a vaporizer set at 40° C. The reactor was operated at atmosphere pressure for 4 hours and then at 50 psig backpressure for 4 hr, and samples were taken periodically and analyzed to determine % conversion of HFC-244bb, and selectivity to HFO-1234yf. The reactor effluent was analyzed using an on-line GCMS, and the data were listed in Table below; the percentages are mole percent. The data in Table 7 below show the performance of this reaction to make HFO-1234yf via HCl elimination at 460° C.

TABLE 7 Conversion Selectivity Selectivity Back pressure Hours of 244bb to 1234yf to 1233xf (Psig) 1 14.36% 92.09% 4.47% 1.210 2 10.45% 93.23% 3.23% 1.210 3 9.26% 93.04% 3.02% 1.210 4 8.65% 92.80% 3.00% 1.210 5 29.39% 95.81% 1.14% 46.460 6 24.03% 96.78% 0.94% 47.470 7 25.16% 96.92% 0.80% 50.490 8 26.49% 97.05% 0.73% 50.490

Example 8

This example demonstrates the conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst at 480° C. with 1.2 psig and 50 psig back pressure.

An empty Inconel tube (½ inch OD, 0.334″ ID) with a heated zone of about 12 inches was heated to 480° C., and HFC-244bb was fed at 1.2 ml/hour through a vaporizer set at 40° C. The reactor was operated at atmosphere pressure for 5 hours and then at 50 psig backpressure for 4 hr, and samples were taken periodically and analyzed to determine % conversion of HFC-244bb, and selectivity to HFO-1234yf. The reactor effluent was analyzed using an on-line GCMS, and the data were listed in Table below; the percentages are mole percent. The data in Table 8 below show the performance of this reaction to make HFO-1234yf via HCl elimination at 480° C.

TABLE 8 Conversion Selectivity Selectivity Back pressure Hours of 244bb to 1234yf to 1233xf (Psig) 1 22.96% 96.50% 1.21% 1.239 2 22.80% 97.06% 0.92% 1.239 3 22.23% 97.10% 0.82% 1.239 4 23.43% 97.19% 0.74% 1.239 5 24.81% 97.37% 0.68% 1.239 6 38.76% 96.73% 0.81% 49.639 7 42.82% 97.40% 0.49% 49.639 8 42.65% 97.53% 0.43% 49.639 8 42.70% 97.44% 0.40% 49.639

Comparative Example 1

Comparative Example 1 demonstrates the dehydrochlorination of 2-chloro-1,1,1,2-tetrafluoropropane in the presence of an activated carbon catalyst.

An inconel tube (½ inch OD) was filled with 4 cc (1.99 gm) of acid washed PCB Polynesian coconut shell based carbon from Calgon (6-10 mesh). HFC-244bb was fed at 1.04 ml/hour through a vaporizer set at 40° C. using a N₂ sweep of 2.4 sccm (4.0×10⁻⁸ m³) giving a total contact time of about 32 seconds while controlling the reactor temperature at 400° C.

The data in Table 9 show the performance of this process with an activated carbon catalyst to make HFO-1234yf via HCl elimination over the period of 15 hours of operation.

TABLE 9 conversion selectivity selectivity Hours of 244bb 1234yf 1233xf 1 78% 67%  13% 2 75% 59%  18% 3 68% 56%  22% 4 58% 44%  27% 5 51% 31%  35% 6 46% 15%  39% 7 46% 6% 38% 8 47% 3% 32% 9 45% 2% 29% 10 31% 3% 36% 11 21% 5% 64% 12 23% 5% 66% 13 24% 5% 67% 14 24% 6% 73% 15 23% 6% 72%

Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range. 

What is claimed is:
 1. A method for producing a fluoropropene of formula CF₃CF═CH₂, comprising: pyrolyzing a hydrofluorochloropropane of formula CF₃CFClCH₃, in the gas-phase in a reaction vessel, maintained at a temperature of from about 400° C. to 700° C., wherein the selectivity for the production of the fluoropropene is at least 80%, in the absence of a catalyst.
 2. The method of claim 1 wherein, said selectivity for the production of said fluoropropene is at least 80% after about 4 hours of continuous operation.
 3. The method of claim 1 wherein, said selectivity for the production of said fluoropropene is at least 80% after about 12 hours of continuous operation.
 4. The method of claim 1, wherein said selectivity for the production of said fluoropropene is at least 85%.
 5. The method of claim 1, wherein said selectivity for the production of said fluoropropene is at least 95%.
 6. The method of claim 1, wherein the said hydrofluorochloropropane is preheated in a vaporizer at a temperature of from about 30° C. to about 100° C.
 7. The method of claim 1, wherein the said hydrofluorochloropropane fed to the reaction vessel further comprises an inert carrier gas.
 8. The method of claim 7 wherein the inert carrier gas is chosen from nitrogen, argon, helium or carbon dioxide.
 9. The method of claim 1, wherein the temperature of the reaction vessel is maintained in the range from about 400° C. to about 600° C.
 10. The method of claim 1, wherein the pressure in the reaction vessel is maintained at a pressure of from 14 psig to 100 psig.
 11. The method of claim 1, wherein the pressure in the reaction vessel is maintained at a pressure of from 40 psig to 85 psig.
 12. The method of claim 1, wherein the pressure in the reaction vessel is maintained at a pressure of from 14 psig to 100 psig and the temperature of the reaction vessel is maintained in the range from about 400° C. to about 500° C. 